Janna. W9 W39.

W. L. MORGAN ET AL

2,143,36

Filed Sept. 9, 1937

IIIA

70

2,143,361

Patented Jan. 10, 1939

UNITED STATES PATENT OFFICE

2,143,361
METHOD 0F MAKING A PURIFIED- SODIUM
LACTATE

Willard L. Morgan, Calumet City, Ill., and Abra

ham H. Goodman, Hammond, Ind., assignors
to American Maize-Products Company, a cor

poration of Maine

ApplicationSeptember 9, 1937, Serial No. 163,000

11 claims.

(c1. 26o-_535) "

Our invention relates to purified lactates such as

sodium lactate and more particularly to a method

of treating the normally impure lactates to elim

A inate the impurities therefrom and produce a pure

5 stable product of desirable color and which will

not become cloudy upon standing.

The purifying method of our invention is ap

plicable generally to the treatment of lactates to
remove undesirable components and produce
10 stable products. The invention will be described,
however, as applied to sodium lactate since it is

especially responsive to our purifyingtreatment.

When sodium lactate is prepared by the usual
procedure a highly colored yellowish red or

brown product is produced, which upon standing

will develop a hazy appearance with increase in
color due to colloidal precipitation of some of its

components. Also, there will occur frequently

an extensive crystallization of salts from the
20 solution.

These undesirable effects are caused

primarily by impurities remaining in the sodium

lactate after it has been produced in accordance.

with the usual methods. While the type and
amount of impurities _present in the sodium
25 lactate product will depend largely upon the raw
materials and type of equipment used, it is not
practical to produce a purified sodium lactate by
the processes used heretofore. As suggested, the
impurities remaining in the iinal product are
formed
during its manufacture in the usual man
30
ner.

then filtering the solution to remove the precipi

tated sulphides. 'Ihe solution is then treated
with an oxidizing agent, for example hydrogen
peroxide, to oxidize the excess sodium sulphide
into sodium sulphate, which is subsequently re-.

movable by concentration and filtration.' Next

the solution is treated with activated carbon
or similar material to effect removal of any
excess hydrogen peroxide or other oxidizing agent
used. Finally, the sodium lactate solution which 10
is now in relatively pure form is concentrated

suiiiciently to crystallize out calcium lactate and

sodium sulphate which are then removed by
filtration; the resulting clear concentrated sodium
lactate solution is then diluted to the desired 15
strength for example, a 50% solution. By means
of this purifying treatment all of the undesirable
salts and contaminating materials present in the
sodium lactate solution, which are not removed in
the usual method of producing sodium lactate,
are entirely eliminated and the resulting sodium
lactate product is free of the usual undesirable
yellowish red or brown color and will not precipi
tate or crystallize on standing. The application
of the process of this invention may be under
stood more clearly by referring first to the usual
process of manufacturing sodium lactate which
removes some of the impurities present but'does

not effect removal of the metal salts and other

materials that normally give the final product 30
undesired characteristics. The usual procedure

An object of our invention is to produce a

puried stable lactate such as sodium lactate.
Another object of our invention is to provide a

for preparing sodium lactate consists briefly of

the following steps:
First, a carbohydrate material, preferably a

35 process for treating normally impure sodium lac

tate to remove substantially all impurities and

produce lactic acid. The fermentation is carried

render the product stable against color forma

tion and cloudying on exposure.

We have found that the sodium lactateprepared

in
accordance with the usual processes contains
40
certain metal salts, particularly copper and iron
salts, and calcium salts and that these salts give
the product undesired color andlrender it un

stable against colloidal precipitation and crystal,

45 lization over a period of time. A feature of the
process of our invention is to treat the impure
sodium lactate to effect removal therefrom of

these undesirable salts.

The process of our invention which will be
described
more in detail hereinafter comprises
50

generally the following principles: The impure

. sodium lactate is first treated with sodium sul

phide to precipitate the bulk of the copper and

iron salts, maintaining the solution slightly alka
line to prevent formation of colloidal sulphur, and

sugar, is fermented with a suitable bacillus to

out in the presence of a nutrient and an anti-acid

such as calcium carbonate.

The function of the

anti-acid is to continuously adjust the acidity

to the proper pH value during the fermentation 40
cycle, in which lactic acid is rst produced by
the fermenting bacillus. This lactic acid reacts
with the calcium carbonate to form calcium lac
tate. At the end of the fermentation, that is
when practically all ofthe carbohydrates or sugar
have been utilized by the bacillus, there remains
a mixture of calcium lactate, a small amount of
free lactic acid, excess unreacted calcium car

bonate, and the non-utilized p'ortion of the nutri

ent used.

In the next operation commonly referred to as

the killing step, the active organisms, i. e., bacilli,
are killed by heating and all of the lactic acid
radicals are converted into their calcium salts,

i. e., calcium lactate. This is accomplished by

50

2,143,361

heating the fermented liquor at about 180 F.

or higherwith sumcient lime to give the mixture
a pH of 10 to 12, usually a pH of 11. The result
ing calcium lactate liquor is then separated by
filtration from the insoluble matter present.
The calcium lactate liquor at this stage has usu
ally a dark. 'reddish brown color, which can be
partly reduced by bleaching with a. vegetable car
bon. Either the bleached or unbleached liquor
is then converted to sodium lactate by reacting

the liquor with sodium carbonate forming the

insoluble salt, calcium carbonate. The insoluble
calcium carbonate is separated from the alkaline
sodium lactate liquor by illtering and the pH of
the filtered sodium lactate is then adjusted to the
proper value by adding a suitable acid. The sodi
um lactate without further chemical treatment
is concentrated to the desired concentration, usu
ally 50% sodium lactate. Prior to the concentra
tion step or after a partial concentration, bleach
ing of the sodium lactate solution with vegetable

carbon is oftenused.
In the above described method of. producing
sodium lactate, it is to be noted that a killing
step follows the fermentation operation and that
in this step lime was added in suiilcient amount
to raise the pH of the solution to l0 to 12, usually
11. At that pH, a portion of the metals present
in the calcium lactate liquor are precipitated
80 and separated as metal hydroxides. However, in
the presence of hydroxy organic compounds such

and ferrous salts, which are very insoluble. The

formation of these lower valent salts brings about
a colloidal haze or precipitate and gives the so
dium lactate a decided musty or hazy appear

ance, although the initial product may have been Cl

quite clear. These metal salts are also objec

tionable in that they impart intense color to

the sodium lactate. For example, iron (ferric)
lactate, which may be found, has an intense
yellow color. .

One oi the first and important steps in the

process of our invention consists in quantitatively
removing these undesirable metal salts from the
sodium lactate solution. This is done by treating
the 50% sodium lactate solution, after it leaves
the evaporator, with sodium sulphide, which pre
cipitates al1 the copper present and most of the
iron. The sodium sulphide is added in slight ex
cess at a. pH of 8 to 10 and is added all at once.

It is advantageous that the sodium sulphide be 20

present in slight excess to >insure a more com

plete removal of metals. An alkaline pH is ad

vantageous since colloidal sulphur would be

formed if free acid were present. Also, it is im
portant that all of the sodium sulphide be added 25
at one time. If the sodium sulphide is added in

several steps the precipitated metal sulphides

are formed in such a nely divided state that

is almost impossible to separate them from the

sodium lactate solution. However, by adding it 30

all at one time and to an excess, the total precip

as lactic acid, calcium lactate, or sodium lactate,
itate will ?locculate sumciently to be ?llterable.
the precipitation of the metal hydroxides, e. g; ' Preferably the liquors are also hot during this

copper hydroxide and iron hydroxide is not a

quantitative operation.

treatment being about 180 F. to facilitate the

Considerable amounts _occulation and subsequent removal by filtration

of the metals remain in solution with the treated

liquors. The metal salts that are left in the cal
cium lactate liquor at this stage and which im

part color and other undesired properties, remain

40

through the process and are found in the usual

finished product. The effective removal of these

undesirable salts in the killing operation as well
as particularly calcium removal during the treat
ment with sodium carbonate is largely dependent
upon the concentration of the calcium lactate
liquor as explained below. The concentration of
the calcium lactate at the killing step varies from
12 to 15 percent, meaning that there is present
85% or more water in the solution. The amount
50 of metal or calcium salts left in solution at this
point would be the equilibrium concentration of
metal or calcium salts in a comparatively large
amount of water. The concentration of sodium
lactate in the finished solution is about 50%
or higher. To produce a 100 pound quantity of.
50% sodium lactate solution would require 325

pounds of 15% calcium lactate liquor. The

amount of water present in the latter is equal to
227.7 pounds. This amount is decreased ap
60 proximately 4.55 times by the concentration step,

to 50/ pounds of water in the 100 pounds of fin

ished 50% sodium lactate.
The increase in concentration of the soluble
metal salts is proportional to the decrease in the
amount of water present. In the above case this
increase would be equal to approximately 4.55
times the original concentration in the calcium
lactate liquor. Consequently, if the concentra
tion of metal salts is at all appreciable in the
70 original liquors, and it usually is, the concen
trated nal 50 percentl sodium lactate product
will contain a supersaturated solution of the cal
cium, copper and iron salts. On storage these
salts in the presence of sodium lactate are slowly
reduced to their lower valent forms, i. e. cuprous

of the precipitated sulphides.

The sodium lactate liquor at this point has

been freed of metals and is distinctly of a light
color but contains a slight excess of sodium sul

phide. The presence of. free sulphide is objec

tionable for two reasons.

The rst is that on

standing, colloidal sulphur will be produced if the

sodium lactate is made acid. Secondly, sodium
lactate is used in the textile industry as a soften

ing agent during color printing and the presence 45

of free sulphide would change the shade of the
dye used. Further, the odor arising from the
sulphide is objectionable.
The free sulphide is removed by oxidation of
the sodium sulphide to sodium sulphate with 50

preferably hydrogen peroxide, or with other oxi

dizing agents such as hypochlorites. An excess
of the oxidizing agent is desirable for quanti

tatively oxidizing the sodium sulphide to sodium

sulphate. When hydrogen peroxide is used as
the oxidizing agent it serves the additional pur
pose of reducing the color of the sodium lactate
liquor by a bleaching action at the same time it

is oxidizing the sodium sulphide.

The presence of the unused or excess hydro
gen peroxide is objectionable for the same reason
as was excess sodium sulphide, in that hydrogen
peroxide also affects the shades of dyes in color
printing. The excess of hydrogen peroxide is

removed by treating the liquors with activated

carbon which catalytically destroys the excess
hydrogen peroxide. Besides removing the last
traces of, peroxide the carbon further bleaches
the sodium lactate liquor, giving a lighter, purer
product.

65

In the above described steps the excess sodium

sulphide was oxidized to sodium sulphate and '

that salt remains in the sodium lactate solution.

This normally causes no diiliculties unless con

centrated solutions of over 50% sodium lactate 75

2,143,361
are desired.

In concentrated sodium lactate

solutions the solubility of sodium sulphate and

also calcium lactate, the formation of which is
explained below, decreases very rapidly between
50% and 60% concentrations of sodium lactate
and at concentrations of 60% to 70% the solu
bility becomes extremely' small.` This will be
easily recognized by referring to the curve in
the accompanying drawing. As shown on this
'10 curve, the solubility of the sodium sulphate in
sodium lactate solution decreases from about
1.4% at a 50% sodium lactate concentration, to
about 0.05% at a 60% sodium lactate concen-l
tration. For the same change in sodium lactate
15 concentration the solubility of calcium lactate
decreases from over 3% to about 0.15%. Thus
in solutions of sodium lactate of over 50% con
centration and especially over 60% concentra

tion, the sodium~ sulphate and calcium lactate

would tend to crystallize and separate out of the
solution and give the sodium lactate undesired

properties.

als present. The excess sodium sulphide is then

oxidized by hydrogen peroxide. To oxidize and

remove the 5 pounds excess sodium sulfide re

quires 9 pounds oi 100% hydrogen peroxide or 30

pounds of 30% hydrogen peroxide. Actually, We
have found the use of 45 to 100 pounds of 30%
hydrogen peroxide to be desirable inasmuch. as
the excess peroxide bleaches the color of the so
dium lactate solution. The treated liquor is then
further bleached and the excess peroxide re 10

moved by adding 100 pounds of vegetable carbon

and filtering. The resulting light-colored liquor
is then'concentrated to 65% sodium lactate in
a vacuum evaporator, at which concentration
the sodium sulphate and calcium lactate salts are

precipitated` and filtered out.

The remaining

clear concentrated sodium lactate solution is then

diluted to 50% sodium lactate.

It will be understood that the foregoing descrip
tion of our process is given only by way of ex 20

ample, and that various rchanges and modifica

tions may be made without departingfrom the

ll`he above discussed calcium lactate is present

because of the incomplete reaction of the fer
mented calcium lactate liquors with the sodium

scope of our invention. The process may b_e ap

carbonate as described hereinabove.

tassium, ammonium, or amine lactates. Likewise,

the sodium sulphide, hydrogen peroxide, and acti

This re

maining calcium lactate is particularly objec

tionable in that it gives a double salt with so

dium lactate that crystallizes out ina very bulky

form. The sodium sulphate which is formed in
the removal of the metal impurities as described
above, will also usually cause a precipitation in
sodium lactate of concentrations of 55% or above.
The time required for these salts to crystallize out

varies with the purity of the sodium lactate. The

purer the sodium lactate the easier and quicker
is the crystallization. The presence of caramel
coloring, dextrins or other free carbohydrate im
purities tends to retard the crystallization and
40 seems to hold a higher supersaturation of cal
cium lactate and sodium sulphate vin solution.
By our additional carbon treatments we decrease
by adsorption the amounts of these bodies which
retard these crystallizations and thus our purer

sodium lactate solutions if concentrated develop

crystalsV in contrast to the more impure prior
known solutions.
We have found that in our initial purified so

dium lactate product the sodium sulphate and

calcium lactate are so near saturation or super

saturation that when the product is further puri

ed and concentrated to above 50 to 55 percent
sodium lactate, the sodium Isulphate and calcium
lactate crystallize on standing. These salts may
therefore be removed from the purified sodium

plied to other lactates thanV sodium lactate.` For

example, we may purify in a similar manner, po- ~

vated carbon used for purposes above described

may be substituted by various lother materials
having an equivalent function. As an example, 30
we may use other water soluble sulphdes such
as barium sulphide the excess of which is removed
as insoluble barium sulphate after treatment

with peroxide.` It will be understood that when

lactates other than sodium lactate are to be puri
fied the sodium sulphide will be substituted when
ever necessary by a precipitating agent compati
ble with the product uses and lactate being puri
fied. Some of the novel features of this inven
tion are defined in the appended claims.
We claim:

<

1. A process of making a purified stable sodium

lactate comprising treating impure sodium lactate

with sodium sulphide to effect precipitation of
the foreign metal salts, removing the precipitated 45
salts, oxidizing the excess sodium sulphide into
sodium sulphate, such oxidizing being effected
with a soluble oxidizing agent capable of being

catalytically dissociated by carbon, removing ex

cess oxidizing agent by treatment with carbon,
concentrating the resulting sodium lactate con
taining said sodium sulphate in solution, to cause
said sodium sulphate to crystallize, and removing
said crystallized sodium sulphate.
2. A process of making a purified stable sodium

lactate by over-concentrating the sodium lactate lactate comprising treating impure sodium lac
solution, for example, to 60 to 75 percent sodium tate with sodium sulphide to precipitate the cop
lactate, to cause the salts to crystallize and then perand iron salts, filtering the solution to re
filtering oil the salts leaving a clear liquor. This -move said salts, oxidizing the excess sodium sul
solution is then diluted back to a 50% sodium phide with hydrogen peroxide to form sodium
sulphate, removing any excess of the hydrogen
lactate strength. In this manner a purified so
peroxide, concentrating the resulting sodium lac
dium lactate is produced that will hold up in
definitely as a clear product on exposure inas

tate solution to cause said sodium sulphate to pre

much as the 50% sodium lactate is then not satu

rated with the sodium sulphate and calcium lac
tate salts.
In accordance with the illustrative but non

cipitate and removing said sodium sulphate.

3. A process of making a purified stable sodium
lactate comprising treating the usual impure so
dium lactate with sodium sulphide to precipitate
the foreign metal salts including copper and iron,
filtering to remove the precipitated salts, oxidiz
ing the -excess sodium sulphide into sodium sul 7.
phate with hydrogen peroxide, treating the l

limiting embodiment of our invention, the desired

puried sodium lactate product may be obtained

70 as follows:
Approximately 2500 gallons of 12 to 15% so
dium lactate produced from dextrose by the proc
esses described hereinabove are treated with 50

tered solution with activated carbon to remove

any excess of the hydrogen peroxide, concen

pounds of sodium sulfide, of which 5 pounds is

15 in excess of that required to precipitate the met

trating the resulting sodium lactate solution suf

ciently to crystallize said sodium sulphate and

2,143,301

other undesired salts, filtering to remove the

crystallized salts, and diluting the resulting con

centrated sodium lactate.
4. A process of preparing a puried stable so
dium lactate comprising treating impure sodium
lactate, containing copper and iron salts, with
an alkaline sulphide solution to precipitate said

//salts, said sulphide solution being present in ex

7. In the process of preparing puried stable

sodium lactate from the usua1 impure sodium lac

tate, the steps of treating said impure sodium

lactate with sodium sulphide to precipitate the
undesired metal salts present therein so that said
salts may be removed, the sodium sulphide being
used in excess to effect quantitative precipitation
of said salts and being alkaline to prevent forma
tion of colloidal sulphur and oxidizing the excess
sodium sulphide into sodium sulphate which can

cess amount to prohibit formation of colloidal

metal sulphides, oxidizing the excess sulphide into
sulphate with an excess of soluble oxidizing agent

be removed subsequently by concentration and

capable of being absorbed by carbon, treating the

filtration.

remaining solution with vegetable carbon to re

move the excess of the oxidizing agent, concen

sodium lactate from partially purified sodium

trating the resulting sodium lactate solution to

eiect crystallization of said sulphate and of any
calcium lactate salts present therein, iiltering to
remove said crystallized salts and diluting the
resulting purified sodium lactate to the desired
concentration.
5. A process of making a purified stable sodium
lactate comprising treating impure sodium lac

8. In> the process of preparing puried, stable

lactate substantially free of heavy metal salts but

containing sodium sulphate and calcium lactate,

the step of concentrating the sodium lactate so
lution to at least about 60% sodium lactate to
precipitate said sodium sulphate and calcium lac
tate so that they may be removed from said 20
sodium lactate solution.
9. In a process of preparing a puried stable

tate with a water soluble sulphide to precipitate

sodium lactate by treating impure sodium lac

the foreign metal salts, removing the precipitated

salts, oxidizing the excess sulphide into sulphate

the impure sodium. lactate with excess of water

with an oxidizing agent selected from the group

soluble sulphide to precipitate foreign metal salts

consisting of hydrogen peroxide and hypochlo

which can be removed by ltration and oxidizing

said excess sulphide into sulphate with a soluble

rites, removing any excess of the oxidizing agent

with carbon, and concentrating the resulting so
dium lactate solution to precipitate said sulphate
and other undesired salts and removing said salts.
6. A process of preparing a puried stable lac
tate of the class consisting of sodium, potassium,
ammonium and amine lactates, comprising treat
ing the impure lactate with a suitable water solu

ble sulphide to precipitate the foreign metal salts,

removing the precipitated salts, treating the re
maining lactate solution with a soluble oxidizing
agent which is non-toxic and is capable of being

19

tate the improvement which comprises treating

oxidizing agent capable of being catalytically dis

sociated by carbon.
10. A process of making a purified stable so

dium lactate comprising treating impure sodium

lactate with a water soluble sulphide to precipi
tate foreign metal salts filtering the solution to
remove said salts oxidizing the excess sulphide I

with an oxidizing agent selected from the group

consisting of hydrogen peroxide and hypochlor

ites and removing any excess of said oxidizing

absorbed by vegetable carbon to convert the ex- . agent by treatment with carbon.
ll. A process as dened in claim 4, in which 40
cess sulphide into sulphate, treating the lactate
the
treatment with alkaline sulphide is carried
solution containing said sulphate with an absorb
out at a pH of about 8 to 10.
ing material to remove any excess of the oxidiz
ing agent, concentrating the resulting lactate so

. lution to precipitate said sulphate and other crys

tallizable salts and removing said salts.

WILLARD L. MORGAN.
ABRAHAM H. GOODMAN.